Influence of Substituents on the Electronic Structure of Mono- and Bis(phosphido) Thorium(IV) Complexes

Rungthanaphatsophon, Pokpong; Duignan, Thomas J.; Myers, Alexander J.; Vilanova, Sean P.; Barnes, Charles L.; Autschbach, Jochen; Batista, Enrique R.; Yang, Ping; Walensky, Justin R.

doi:10.1021/acs.inorgchem.8b00922

Title: Influence of Substituents on the Electronic Structure of Mono- and Bis(phosphido) Thorium(IV) Complexes

Journal Article · 01 June 2018 · Inorganic Chemistry

DOI: https://doi.org/10.1021/acs.inorgchem.8b00922 · OSTI ID:1483515

Rungthanaphatsophon, Pokpong ^[1]; Duignan, Thomas J. ^[2]; Myers, Alexander J. ^[1]; Vilanova, Sean P. ^[1]; Barnes, Charles L. ^[1];

^[3];

^[4];

^[1]

Univ. of Missouri, Columbia, MO (United States). Dept. of Chemistry
Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Univ. at Buffalo, NY (United States). Dept. of Chemistry
Univ. at Buffalo, NY (United States). Dept. of Chemistry
Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

Here, a series of metallocene thorium complexes with mono- and bis(phosphido) ligands have been investigated with varying hues: (C₅Me₅)₂Th(Cl)[P(Mes)₂] (Mes = mesityl = 2,4,6-(CH₃)₃C₆H₂; dark red-purple), (C₅Me₅)₂Th[P(Mes)(CH₃)]₂ (dark red-purple), (C₅Me₅)₂Th(CH₃)[P(Mes)₂] (dark red-purple), (C₅Me₅)₂Th(CH₃)[P(Mes)(SiMe₃)] (orange), (C₅Me₅)₂Th(Cl)[P(Mes)(SiMe₃)] (orange), (C₅Me₅)₂Th[P(Mes)(SiMe₃)]₂ (orange), and (C₅Me₅)₂Th[PH(Mes)]₂ (pale yellow). While all of these complexes bear a mesityl group on phosphorus, the electronic structure observed differs depending on the other substituent (mesityl, methyl, trimethylsilyl, or hydrogen). This sparked an investigation of the electronic structure of these complexes using ³¹P NMR and electronic absorption spectroscopy in concert with time-dependent density functional theory calculations.

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Research Organization:: Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: 89233218CNA000001

OSTI ID:: 1483515

Report Number(s):: LA-UR--18-22942

Journal Information:: Inorganic Chemistry, Journal Name: Inorganic Chemistry Journal Issue: 12 Vol. 57; ISSN 0020-1669

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Experimental and computational studies on a three-membered diphosphido thorium metallaheterocycle [η ⁵ -1,3-(Me ₃ C) ₂ C ₅ H ₃ ] ₂ Th[η ² -P ₂ (2,4,6- ⁱ Pr ₃ C ₆ H ₂ ) ₂ ] Zhang, Congcong; Wang, Yongsong; Hou, Guohua Dalton Transactions, Vol. 48, Issue 20 https://doi.org/10.1039/c9dt01160a	journal	January 2019
Thorium(IV) and Uranium(IV) Phosphaazaallenes Rungthanaphatsophon, Pokpong; Fajen, O. Jonathan; Kelley, Steven P. Inorganics, Vol. 7, Issue 9 https://doi.org/10.3390/inorganics7090105	journal	August 2019

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